01529nas a2200241 4500008004100000022001400041245007800055210006900133260000800202300001200210490000700222520076900229653003300998653001201031653002201043653001301065653001401078100001801092700002201110700002601132700002501158856010401183 2020 eng d a2155-543500aManganese-catalyzed alpha-olefination of nitriles with secondary alcohols0 aManganesecatalyzed alphaolefination of nitriles with secondary a cJAN a947-9540 v103 a
An expedient catalytic approach for alpha-olefination of nitriles using secondary alcohols with the liberation of molecular hydrogen and water as the only byproducts is reported. This reaction is catalyzed by a molecularly defined manganese(I) pincer complex and operates in the absence of any hydrogen acceptors. A broad range of substrates including cyclic, acyclic, and benzylic alcohols, as well as various nitrile derivatives, such as arylmethyl and heteroarylmethyl nitriles, are employed in the reaction to provide a diverse range of alpha-vinyl nitriles in good to excellent yields. Mechanistic studies showed that the reaction proceeds via dehydrogenative pathway and the activation of alpha(C-H) bond of the alcohol is the rate-determining step.
10aacceptorless dehydrogenation10aAlcohol10aalpha-olefination10aHydrogen10amanganese1 aYadav, Vinita1 aLandge, Vinod, G.1 aSubaramanian, Murugan1 aBalaraman, Ekambaram uhttp://library.ncl.res.in/content/manganese-catalyzed-alpha-olefination-nitriles-secondary-alcohols